CHEM-5215

Dr. Bushra Javaid

 Carbohydrates or Saccharides (Greek Sakcharon meaning "Sugar")
 Most abundant organic molecules in nature-composed of Carbon, Hydrogen and oxygen.
 Many Carbohydrates also contain Nitrogen and other elements.
 The name carbohydrate literally means ‘hydrates of carbon’. But not always considered
 Produced by plants during photosynthesis
 After eating plant foods, humans convert the carbohydrates into glucose
 Glucose
 Most abundant carbohydrate
 Preferred source of energy for the blood, brain, and nervous system

 Carbohydrate-rich plant foods make up the foundation of diets all over the world

Carbohydrates may be defined as polyhydroxyaldehydes or

ketones or compounds which produce them on hydrolysis. 2
1. They are the most abundant dietary source of energy (4 Cal/g) for all
organisms.
2. Carbohydrates are precursors for many organic compounds (fats, amino
acids).
3. Carbohydrates (as glycoproteins and glycolipids) participate in the
structure of cell membrane and cellular functions such as cell growth,
adhesion and fertilization.
4. They are structural components of many organisms. These include the fiber
(cellulose) of plants, exoskeleton of some insects and the cell wall of
microorganisms.
5. Carbohydrates also serve as the storage form of energy (glycogen/starch)
to meet the immediate energy demands of the cell
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  Simple carbohydrates
 Monosaccharide
 Oligosaccharides
 Disaccharide
 Perceived as sweeter than complex carbohydrates
 Mixes with saliva and reacts with taste buds

 Complex carbohydrates
 Polysaccharides

Mono- and oligosaccharides are sweet to taste, crystalline in character and

soluble in water, hence they are commonly known as sugars
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 Monosaccharides (Greek : mono-one) are the simplest group of carbohydrates and are often
referred to as simple sugars.
 They have the general formula Cn(H2O)n, and they cannot be further hydrolysed.
 The monosaccharides are divided into different categories, based on
 The functional group
 The number of carbon atoms

 Aldoses
 When the functional group in monosaccharides is an aldehyde (H-C=O), they are known as aldoses
e.g. glyceraldehyde, glucose.
 Ketoses
 When the functional group is a keto (C=O) group, they are referred to as ketoses e.g.
dihydroxyacetone, fructose.

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• Based on the number of carbon atoms, the monosaccharides are regarded as trioses (3C),
tetroses (4C), pentoses (5C), hexoses (6C) and heptoses (7C).
• These terms along with functional groups are used while naming monosaccharides. For
instance, glucose is an aldohexose while fructose is a ketohexose

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 Oligosaccharides (Greek: oligo-few) contain 2-10 monosaccharide molecules
which are liberated on hydrolysis.
 Based on the number of monosaccharide units present, the oligosaccharides are
further subdivided to disaccharides, trisaccharides etc.
 Three Disaccharides
 Sucrose
 Most common
 Lactose
 Maltose
 Least common
 Formed from digestion of starches

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Figure 4.3
 Polysaccharides (Greek: poly-many) are polymers of
monosaccharide units with high molecular weight (up to a
million).
 They are usually tasteless (non-sugars) and form colloids
with water.
 The polysaccharides are of two types
 homopolysaccharides
 heteropolysaccharides

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 Stereoisomerism is an important character of monosaccharides.
 Stereoisomers are the compounds that have the same structural formulae but differ
in their spatial configuration.
 A carbon is said to be asymmetric when it is attached to four different atoms or
groups.
 The number of asymmetric carbon atoms (n) determines the possible isomers of a
given compound which is equal to 2n.
 Glucose contains 4 asymmetric carbons, and thus has 16 isomers.

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 Glyceraldehyde (triose) is the simplest monosaccharide with one
asymmetric carbon atom.

 It exists as two stereoisomers- reference carbohydrate to

represent the structure of all other carbohydrates.

 The D and L isomers are mirror images of each other.

 The spatial orientation of H and OH groups on the carbon atom

(C5 for glucose) that is adjacent to the terminal primary alcohol
carbon determines whether the sugar is D- or L-isomer.
 If the OH group is on the right side, the sugar is of D-series
 if on the left side, it belongs to L-series

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o The configuration of possible D-aldoses
starting from D-glyceraldehyde is
depicted

o This is a representation of Killiani-Fischer

synthesis, by increasing the chain length
of an aldose, by one carbon at a time.

o Thus, starting with an aldotriose (3C),

aldotetroses (4C), aldopentoses (5C) and
aldohexoses (6C) are formed.

o Of the 8 aldohexoses, glucose, mannose

and galactose are the most familiar.

o Among these, D-glucose is the only

aldose monosaccharide that
predominantly occurs in nature. 13
Starting from dihydroxyacetone (triose), there are five keto-sugars which are
physiologically important.

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 If two monosaccharides differ from each other in their
configuration around a single specific carbon (other than
anomeric) atom, they are referred to as epimers to each other
 For instance, glucose and galactose are epimers with regard to
carbon 4 (C4-epimers).
 That is, they differ in the arrangement of OH group at C4.
 Glucose and mannose are epimers with regard to carbon 2 (C2-
epimers).
 The interconversion of epimers is known as epimerization
 group of enzymes—namely—epimerases catalyse this reaction.
 Enantiomers are a special type of stereoisomers that are mirror
images of each other.

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 The hydroxyl group of monosaccharides can react with its own aldehyde or keto
functional group to form hemiacetal and hemiketal

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 D-glucose exists in solution as an
intramolecular hemiacetal
 In which the free hydroxyl group at
C-5 has reacted with the aldehydic
C-1, rendering the latter carbon
asymmetric and producing two
stereoisomers, designated α and β
 These six-membered ring
compounds are called pyranoses
because they resemble the six
membered ring compound pyran

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 Aldohexoses also exist in cyclic
forms having five membered rings,
which, because they resemble the
five membered ring compound furan,
are called furanoses

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Tautomerization or enolization

 The process of shifting a hydrogen

atom from one carbon atom to
another to produce enediols is
known as tautomerization.
 Sugars possessing anomeric carbon
atom undergo tautomerization in
alkaline solutions.
 Glucose form D-fructose and D-
mannose.

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Reducing properties Oxidation

 The sugars are classified as reducing  Depending on the oxidizing agent

or nonreducing used, the terminal aldehyde (or keto)
or the terminal alcohol or both the
 The reducing property is attributed
groups may be oxidized.
to the free aldehyde or keto group
of anomeric carbon  For instance, consider glucose :
 Many tests are employed to identify 1. Oxidation of aldehyde group results
the reducing action of sugars. in the formation of gluconic acid.
 These include Benedict’s test, 2. Oxidation of terminal alcohol group
Fehling’s test, Barfoed’s test etc. leads to the production of glucuronic
acid.

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Reduction Dehydration

 When treated with reducing agents  When treated with concentrated

such as sodium amalgam, the aldehyde sulfuric acid, monosaccharides
or keto group of monosaccharide is undergo dehydration with an
reduced to corresponding alcohol elimination of 3 water molecules.
 Thus hexoses give hydroxymethyl
furfural while pentoses give furfural on
dehydration
 These furfurals can condense with
phenolic compounds (α-naphthol) to
form coloured products.
 This is the chemical basis of the
popular Molisch test.
 Sorbitol and dulcitol when accumulate
in tissues in large amounts cause strong
osmotic effects leading to swelling of 21
cells
 Disaccharide consists of two monosaccharide units (similar or dissimilar) held
together by a glycosidic bond
 They are crystalline, water-soluble and sweet to taste. The disaccharides are of two
types
 Reducing disaccharides with free aldehyde or keto group e.g. maltose, lactose.
 Non-reducing disaccharides with no free aldehyde or keto group e.g. sucrose,
trehalose.
 Maltose
 Maltose is composed of two α-D-glucose units held together by α(1-4)glycosidic bond.
 The free aldehyde group present on C1 of second glucose answers the reducing reactions

 Lactose
 Lactose is more commonly known as milk sugar since it is the disaccharide found in milk
 Lactose is composed of β D-galactose and β D-glucose held together by β(1-4) glycosidic bond.
The anomeric carbon of C1 glucose is free, hence lactose exhibits reducing properties
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Sucrose
 Sucrose (cane sugar) is the sugar of commerce, mostly produced by sugar cane and sugar
beets.
 Sucrose is made up of α-D-glucose and β-D-fructose.
 The two monosaccharides are held together by a glycosidic bond α1-β2, between C1 of glucose
and C2 of fructose.
 The reducing groups of glucose and fructose are involved in glycosidic bond, hence sucrose is a
non-reducing sugar
 Sucrose is an important source of dietary carbohydrate.
 It is sweeter than most other common sugars (except fructose) namely glucose, lactose and
maltose.
 Sucrose is employed as a sweetening agent in food industry.
 The intestinal enzyme—sucrase—hydrolyses sucrose to glucose and fructose which are
absorbed.
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 Polysaccharides (or simply glycans) consist of repeat units of monosaccharides or their
derivatives, held together by glycosidic bonds
 They are primarily concerned with two important functions-
 structural
 storage of energy

 Polysaccharides are linear as well as branched polymers.

 This is in contrast to structure of proteins and nucleic acids which are only linear polymers.
 The occurrence of branches in polysaccharides is due to the fact that glycosidic linkages
can be formed at any one of the hydroxyl groups of a monosaccharide.
 Polysaccharides are of two types
1. Homopolysaccharides on hydrolysis yield only a single type of monosaccharide.
They are named based on the nature of the monosaccharide.
 Thus, glucans are polymers of glucose whereas fructosans are polymers of fructose

2. Heteropolysaccharides on hydrolysis yield a mixture of a few monosaccharides or

their derivatives 25
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 Starch is the carbohydrate reserve of plants which is the most important dietary source
for higher animals, including man.
 High content of starch is found in cereals, roots, tubers, vegetables etc
 Starch is a homopolymer composed of D-glucose units held by glycosidic bonds. It is
known as glucosan or glucan.
 Starch consists of two polysaccharide components-water soluble amylose (15-20%)
and a water insoluble amylopectin (80-85%).
 Chemically, amylose is a long unbranched chain with 200–1,000 D-glucose units held
by a(14) glycosidic linkages.
 Amylopectin, on the other hand, is a branched chain with a(16) glycosidic bonds at
the branching points and a(14) linkages everywhere else
 Amylopectin molecule containing a few thousand glucose units looks like a branched
tree (20–30 glucose units per branch)

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 • Starches are hydrolysed by amylase
(pancreatic or salivary) to liberate dextrins, and
finally maltose and glucose units.
• Amylase acts specifically on a(14) glycosidic
bonds.

Dextrins
Dextrins are the breakdown products of starch by the
enzyme amylase or dilute acids.

Dextrans
Dextrans are polymers of glucose, produced by
microorganisms.

Inulin
Inulin is a polymer of fructose i.e., fructosan.
It occurs in garlic, onion etc.
It is a low molecular weight (around 5,000) polysaccharide easily soluble in
water.
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 Glycogen is the carbohydrate reserve in animals, hence often referred to as
animal starch
 It is present in high concentration in liver, followed by muscle, brain etc.
 Glycogen is also found in plants that do not possess chlorophyll (e.g. yeast, fungi)
 The structure of glycogen is similar to that of amylopectin with more number of
branches
 Glucose is the repeating unit in glycogen joined together by a(14) glycosidic
bonds, and a(16) glycosidic bonds at branching points
 The molecular weight and the number of glucose units vary in glycogen
depending on the source from which glycogen is obtained

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 Cellulose, a major constituent of plant cell walls, consists of long linear chains of glucose with
b(14) linkages
 Every other glucose is flipped over, due to b linkages
 This promotes intra-chain and inter-chain H-bonds and van der Waals interactions, that cause
cellulose chains to be straight & rigid, and pack with a crystalline arrangement in thick bundles -
microfibrils
 Cellulose cannot be digested by mammals— including man—due to lack of the enzyme that
cleaves b(14) glycosidic bonds
 Certain ruminants and herbivorous animals contain microorganisms in the gut which produce
enzymes that can cleave b(14) glycosidic bonds
 Hydrolysis of cellulose yields a disaccharide cellobiose, followed by b D-glucose

CH 2OH 6CH OH CH 2OH CH 2OH CH 2OH

2
O 5 O O H O H O OH
H H H
H H H H H
OH H 1 O 4 OH H 1 O OH H O OH H O OH H
OH H H H
H 2 H
3
H OH H OH H OH H OH H OH
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cellulose
 Chitin is composed of N-acetyl D glucosamine units held together by b(14)
glycosidic bonds.
 It is a structural polysaccharide found in the exoskeleton of some invertebrates e.g.
insects, crustaceans.
 Chitin looks like cellulose but carbon 2 has an amino group that is acetlylated.

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 Mucopolysaccharides are heteroglycans made up of repeating units of sugar derivatives, namely
amino sugars and uronic acids.
 These are more commonly known as glycosaminoglycans (GAG).
 Acetylated amino groups, besides sulfate and carboxyl groups are generally present in GAG
structure.
 The presence of sulfate and carboxyl groups contributes to acidity of the molecules, making
them acid mucopolysaccharides.
 Some of the mucopolysaccharides are found in combination with proteins to form mucoproteins
or mucoids or proteoglycans.
 Mucoproteins may contain up to 95% carbohydrate and 5% protein.

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• Mucopolysaccharides are essential
components of tissue structure.
• The extracellular spaces of tissue
(particularly connective tissue-cartilage,
skin, blood vessels, tendons) consist of
collagen and elastin fibers embedded in a
matrix or ground substance.
• The ground substance is predominantly
composed of GAG.
• The important mucopolysaccharides
include hyaluronic acid, chondroitin 4-
sulfate, heparin, dermatan sulfate and
keratan sulfate
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 Proteoglycans are macromolecules of the cell surface or extracellular matrix.
 One or more glycosaminoglycan chains are joined covalently to a membrane protein or a
secreted protein.
 The glycosaminoglycan moiety commonly forms the greater fraction (by mass) of the
proteoglycan molecule, dominates the structure, and is often the main site of biological
activity.
 Proteoglycans are major components of connective tissue such as cartilage, in which their
many noncovalent interactions with other proteoglycans, proteins, and glycosaminoglycans
provide strength and resilience.

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 Glycoproteins are carbohydrate-protein conjugates in which the glycans are smaller, branched,
and more structurally diverse than the huge glycosaminoglycans present in proteoglycans.
 Two broad classes of glycoproteins occur in nature—
 the O-linked and the N-linked glycoproteins
 In O-linked glycoproteins, the carbohydrate is attached at its anomeric carbon through a
glycosidic linkage to the -OH group of a Ser or Thr residue.
 In an N-linked glycoprotein, the carbohydrate is attached via an N-glycosyl linkage to the
amide nitrogen of an Asn residue of the protein.
 N-linked oligosaccharide chains are attached at Asn residues that are part of the consensus
sequence -N-{P}-[ST]-, although not all such sequences in proteins are modified.
 There appears to be no specific consensus sequence for the attachment of O-linked
oligosaccharides.

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 Glycolipids are membrane lipids in which the hydrophilic head groups are
oligosaccharides, which, as in glycoproteins, act as specific sites for recognition by
carbohydrate-binding proteins.

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